Thermoplastic resin composition

ABSTRACT

A novel thermoplastic resin composition excellent in heat resistance, mechanical properties and processability is provided which comprises a composition containing (A) a dispersing phase of polyphenylene ether obtained by oxidation polymerization of at least one phenol compound represented by the formula: ##STR1## wherein R 1 , R 2 , R 3 , R 4  and R 5  each represents a hydrogen atom, a halogen atom or a substituted or unsubstituted hydrocarbon residue and at least one of them is a hydrogen atom and (B) a crystalline thermoplastic resin matrix phase and (C) a mutual compatibilizer compatible with (A) and/or (B), an average particle diameter in said dispersing phase having of 0.01-10 μ.

RELATED APPLICATION

This is a continuation of U.S. application of U.S. Ser. No. 07/102,528filed Sep. 29, 1987, now abandoned.

This invention relates to a novel thermoplastic resin compositionsuitable for shaped articles, sheet or film by injection molding orextrusion molding. More particularly, it relates to a novelthermoplastic resin composition superior in heat resistance, mechanicalproperties and processability, which contains a mutual compatibilizer ina resin composition containing a dispersing phase of polyphenylene etherand a crystalline thermoplastic resin matrix phase.

Polyphenylene ether is thermoplastic resin superior in variousmechanical properties, heat resistance, electrical properties, chemicalresistance, hot water resistance, flame resistance and dimensionstability, but inferior in processability due to high melt viscosity andrelatively inferior in impact resistance.

A composition material comprising polyphenylene ether and polystyrene isproposed in order to lessen melt viscosity of polyphenylene ether and toimprove processability thereof, leaving various other good properties ofpolyphenylene ether unchanged. However, such inherent good properties ofpolyphenylene as heat resistance, flame resistance and chemicalresistance are somewhat damaged when enough polystyrene is added toprovide processability practically. No sufficient improvement is seen inimpact resistance, either, even after polystyrnee is added.

On the other hand, crystalline thermoplastic resins are usually superiorin heat resistance, stiffness, strength and oil resistance, but areinferior in impact resistance in many cases. In order to improve theimpact strength of the resins, rubber components are blended orcopolymerized therewith to result in much reduction of heat resistanceand surface hardness. Further, crystalline thermoplastic resins whenmolten decrease in viscosity and can readily be molded. However, whenthey are molded at temperatures even slightly lower than theircrystallizing solidification temperature, they are rapidly hardend andthus are narrow in range of molding conditions. Moreover, they areconspicuous in change of properties and size at practical use. Further,most of heat resistant crystalline thermoplastic resins are high insusceptibility to water and not only change in properties and dimension,but are inferior in appearance.

Development is expected in new applications if a resin composition isprepared in which polyphenylene ether and a crystalline thermoplasticresin are blended, maintaining favorite properties of both componentsand having improved processability and impact strength. However,polyphenylene ether and crystalline thermoplastic resin are greatlydifferent in melt viscosity from each other and they are very poor incompatibility. Simple blending of them encounters the followingdifficulties:

1. hardness in stable take-up of strands extruded and greatly lowerprocessability in molding, because their melt viscosity difference isvery large; and

2. no improvement in mechanical properties of the shaped articles,particularly in impact resistance, but rather lower than expected on thebasis of their respective values.

One approach to solve these problems is addition of additives havingreactivity or compatibility to system of polyphenylene ether andpolyamide as disclosed in Japanese Patent Publication (Kokoku) No.60-11966 and Japanese Patent Publication (Kokai) Nos. 56-47432, 57-10642and 60-58463. Especially, the methods disclosed in Japanese PatentPublication (Kokoku) No. 60-11966 and Japanese Patent Publication(Kokai) No. 56-47432 afford good effect, but impact strength is stillnot enough.

Furthermore, Japanese Patent Publication (Kokai) Nos. 56-49753,57-10642, 57-165448 and 59-66452 disclose use of additives reactive withmodified polystyrene, polyphenylene ether or rubber. However, dispersephase is not clear and even when polyphenylen ether is disperse phase,no mention is made of particle size. Such composition is out of balancebetween impact resistance and heat resistance and besides improvement ofimpact resistance is still not sufficient.

After a study on a resin composition of polyphenylene ether andcrystalline thermoplastic resin, we have found that a resin compositionhaving good balance between heat resistance and impact resistance,markedly improved impact resistance and superior processability isobtained by adding a mutual compatibilizer (C) to a composition of apolyphenylene ether disperse phase (A) and a crystalline thermoplasticresin matrix phase (B) with specifying particle size of said dispersephase.

That is, this invention relates to a thermoplastic resin compositionwhich comprises a composition comprising (A) a dispersing phase, (B)matrix phase and (C) a mutual compatibilizer defined below and in whichaverage particle size in the dispersing phase is 0.01-10μ:

(A): a dispersing phase comprising polyphenylene ether obtained byoxidation polymerization of at least one phenol compound represented bythe formula: ##STR2## wherein R₁, R₂, R₃, R₄ and R₅ each represents ahydrogen atom, a halogen atom or a substituted or unsubstitutedhydrocarbon residue and at least one of them is a hydrogen atom;

(B) a crystalline thermoplastic resin matrix phase; and

(C) a mutual compatibilizer compatible with (A) and/or (B).

Polyphenylene ether for (A) is polymer obtained, for example, byoxidation polymerization of one or more of phenol compounds having theformula: ##STR3## wherein R₁, R₂, R₃, R₄ and R₅ each represents ahydrogen atom, a halogen atom or a hydrocarbon residue substituted ornot and at least one of them is a hydrogen atom, with molecular oxygenor gas containing the same in the presence of an oxidation couplingcatalyst.

Examples of R₁ -R₅ are a hydrogen atom, a chlorine atom, a bromineatome, a fluorine atom, an iodine atom, a methyl group, an ethyl group,an n- or iso-propyl group, a pri.-, sec.- or tert.-butyl group, achloroethyl group, a hydroxyethyl group, a phenylethyl group, a benzylgroup, a hydroxymethyl group, a carboxyethyl group, amethoxycarbonylethyl group, a cyanoethyl group, a phenyl group, achlorophenyl group, a methylphenyl group, a dimethylphenyl group, anethylphenyl group or an allyl group.

Examples of phenol compound are phenol, o-, m- or p-cresol, 2,6-, 2,5-,2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol,2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- or2,4,6-trimethylphenol, 3-methyl-6-t. butylphenol, thymol and2-methyl-6-allylphenol. Alternatively, copolymer of any of the phenolcompound listed above and the other phenol compound, for example,polyhydroxy aromatic compound, may be employed. The polyhydroxy aromaticcompound is, for example, bisphenol A, tetrabromobisphenol A, resorcin,hydroquinone and novolack resin.

Preferably polymers are homopolymer of 2,6-dimethylphenol or2,6-diphenylphenol and copolymers of a large amount of 2,6-xylenol and asmall amount of 3-methyl-6-t-butylphenol or of 2,3,6-trimethylphenol.

Any oxydation coupling catalyst may be employed for oxydationpolymerization of phenol compound, as long as it has polymerizationability. Examples are cuprous compound/tert. amine such as cuprouschloride/triethylamine and cuprous chloride/pyridine; cupriccompound/amide/alkali metal hydroxide such as cupricchloride/pyridine/potassium hydroxide; manganese salt/primary amine suchas manganese chloride/ethanolamine and manganeseacetate/ethylenediamine; manganese salt/alcolate or phenolate such asmanganese chloride/sodium methylate and manganese chloride/sodiumphenolate; and cobalt salt/tert. amine.

Polymerization temperature for preparing polyphenylene ether is 40° C.or higher (high temperature polymerization) or lower (low temperaturepolymerization). Either temperature may be used, although polymersproduced thereby have different properties.

Polyphenylene ether for (A) further includes that grafted with styrenicpolymer or other polymer. For instance, grafted one is obtained bygraft-polymerizing styrene monomer and/or other comonomer in thepresence of polyphenylene ether and organic peroxide (Japanese PatnetPublications (Kokoku) 47-47862, 48-12197, 49-5623, 52-38596 and52-30991) or by melt-kneading polyphenylene ether and polystyrene in thepresence of a radical initiator (Japanese Patent Publication (Kokai)52-142799).

Reduced viscosity of polyphenylene ether for (A) measured in a 0.5 g/dlchloroform solution at 25° C. is preferably 0.40-0.60, more preferably0.45-0.55. When reduced viscosity is less than 0.40 or more than 0.60,impact strength of the composition decreases.

Crystalline thermoplastic resin matrix phase (B) comprises at least oneresin selected from polyethylene, polypropylene, polyamide thermoplasticpolyester, polyacetal, polyphenylene sulfide and polyether ether ketone.

Said polyethylene is crystalline polyethylene and includes low-densitypolyethylene, medium-density polyethylene, high-density polyethylene,straight chain low-density polyethylene, etc.

Said polypropylene is crystalline polypropylene and includes homopolymerof propylene and besides block or random copolymers of propylene with,for example, α-olefins such as ethylene and butene-1.

Preferably, said polypropylene have a melt index of 0.1-100 g/10 min.,especially 0.5-40 g/10 min.

Homopolymer and block or random copolymers of propylene is able toobtain by reaction in the presence of, for example, a catalystcomprising titanium trichloride and an alkylaluminum compound usuallycalled Ziegler-Natta catalyst.

As the polyamides, there may be used those obtained by polycondensationof lactams of three or more membered rings, polymerizable ω-amino acids,dibasic acids with diamines, etc. As typical examples thereof, mentionmay be made of polymers of ε-caprolactam, aminocaproic acid,enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, etc.,polymers obtained by polycondensation of diamines such ashexamethylenediamine, nonamethylenediamine, undecamethylenediamine,dodecamethylenediamine, m-xylylenediamine, etc. with dicarboxylic acidssuch as terephthalic acid, isophthalic acid, adipic acid, sebacic acid,dibasic dodecanoic acid, glutaric acid, etc., or copolymers thereof.

Typical examples of said polyamides are aliphatic polyamides such aspolyamide 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12,polyamide 6,12, etc. and aromatic polyamides such aspolyhexamethylenediamine terephthalamide, polyhexamethylenediamineisophthalamide, xylene group-containing polyamides, etc. These may alsobe used as mixtures or copolymers of two or more of them.

Said thermoplastic polyesters comprise dicarboxylic acid component ofwhich at least 40 mol % is terephthalic acid and diol component. Thedicarboxylic acid component other than terephthalic acid includesaliphatic dicarboxylic acids of 2-20 carbon atoms such as adipic acid,sebacic acid, dodecanedicarboxylic acid, etc., aromatic dicarboxylicacids such as isophthalic acid, naphthalenedicarboxylic acid, etc. andalicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc.These may be used alone or in combination of two or more. As said diolcomponents, mention may be made of, for example, aliphatic glycols,alicyclic glycols and aromatic glycols such as ethylene glycol,1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol,1,4-cyclohexanediol, 4,4'-dihydroxydiphenyl, etc. They may be used aloneor in combination of two or more.

Of these thermoplastic polyesters, especially preferred are polybutyleneterephthalate and polyethylene terephthalate. Preferably, they have anintrinsic viscosity within the range of 0.5-3.0 measured ino-chlorophenol as a solvent at 25° C. and those of intrinsic viscosityoutside said range cannot provide the desired mechanical strength.

The mutual compatibilizer (C) is such that compatible with thepolyphenylene ether dispersing phase (A) and/or the crystallinethermoplastic resin matrix phase (B) and has a function to stabilizeeach of said phases and does not cause poor appearance or deteriorationof properties due to unstable phases at actual use.

As the mutual compatibilizer, surface active agents of low molecularweight and soaps may also be used, but those of high molecular weightare preferred for obtaining stability of the phases. More preferred arethose which can react, even partially, with either one or both of thephases and have not mere affinity therewith, regardless of highmolecular weight or low molecular weight. Further preferably, the mutualcompatibilizer per se has affinity with or is able to react with (A)and/or (B) and has impact absorbing capacity.

As the mutual compatibilizer of low molecular weight, there may be usedat least one compound selected from compounds containing, in themolecule, at least one of carboxyl group, acid anhydride group, acidamide group, imide group, carboxylate group, epoxy group, amino group,isocyanate group, group having oxazoline ring and hydroxyl group.Examples of these compounds are aliphatic carboxylic acids, aromaticcarboxylic acids, esters, acid anhydrides and acid amides of theseacids, imides derived from these acids and/or acid anhydrides, aliphaticglycols or phenols, isocyanates such as toluene diisocyanate andmethylenebis-(4-phenyl isocyanate), oxazolines such as2-vinyl-2-oxazoline, epoxy compounds such as epichlorohydrin andglycidyl methacrylate, aliphatic amines, aliphatic diamines, aliphatictriamines, aliphatic tetramines, aromatic amines such asm-phenylenediamine, 4,4'-methylenedianiline, benzidine, etc. Thefollowing unsaturated compounds are more preferred.

Typical examples are maleic anhydride, maleic acid, fumaric acid,maleimide, maleic acid hydrazide, a reaction product of maleic anhydrideand diamine, e.g., compounds having the formulas ##STR4## wherein R isan aliphatic or aromatic group, methylnadic anhydride, dichloromaleicanhydride, maleic acid amide and, natural fats and oils such as soybeanoil, tung oil, caster oil, linseed oil, hempseed oil, cottonseed oil,sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconutoil and sardine oil; unsaturated carboxylic acid such as acrylic acid,butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid,pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoicacid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid,2-hexenoic acod, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid,α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid,2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid,4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid,9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid,9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid,tetracocenoic acid, mycolipenic acid, 2,4-pentadienic acid,2,4-hexadienic acid, diallyl acetic acid, geranic acid, 2,4-decadienicacid, 2,4-dodecadienic acid, 9,12-hexadecadienic acid,9,12-octadecadienic acid, hexadecatrienic acid, linolic acid, linolenicacid, octadecatrienic acid, eicosadienic acid, eicosatrienic acid,eicosatetraenic acid, ricinoleic acid, eleosteric acid, oleic acid,eicosapentaenic acid, erucic acid, docosadienic acid, docosatrienicacid, docosatetraenic acid, docosapentaenic acid, tetracosenoic acid,hexacosenoic acid, hexacodienoic acid, octacosenoic acid, andtetraaconitic acid; ester, acid amide or anhydride or unsaturatedcarboxylic acid above; unsaturated oxazoline; unsaturated alcohol suchas allyl alcohol, crotyl alcohol, methylvinyl carbinol, allyl carbinol,methylpropenyl carbinol, 4-penten-1-ol, 10-undecene-1-ol, propargylalcohol, 1,4-pentadiene-3-ol, 1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol,2,4-hexadiene-1-ol, alcohol of the formula: C_(n) H_(2n-5) OH, C_(n)H_(2n-7) OH or C_(n) H_(2n-9) OH (n is an integer), 3-butene-1,2-diol,2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol or2,6-octadiene-4,5-diol; and unsaturated amine such as that where an OHgroup of the unsaturated alcohol is replaced by an --NH₂ group.

Isocyanates such as toluene diisocyanate and methylenediphenyldiisocyanate are also included. There may be further included variouspolymers and rubbers of low molecular weight (e.g., 500-10,000) intowhich said compatibilizing agents are introduced.

Mutual compatibilizer of high molecular weight includes polymers of highmolecular weight (e.g., more than 10,000) into which saidcompatibilizers of low molecular weight are introduced. Preferred arepolyethylene, polypropylene and polyolefin copolymers such asethylene-propylene coplymer and ethylene-butene copolyers, and abovementioned polyamides, thermoplastic polyesters, and polyphenylenesulfide, polyacetal and polyether ether ketone into whichcompatibilizing agent of low molecular weight is introduced. Thesepolymers include those copolymerized with other components. Furtherpreferred is at least one selected from modified rubber-like materialand epoxy compounds.

"Modified rubber-like materials" in this invention mean those obtainedby modification of rubber-like materials.

"Rubber-like material" in this invention mean natural and syntheticpolymer materials which are elastic at room temperature.

As examples of the rubber-like materials, mention may be made of naturalrubber, butadiene polymer, butadienestyrene copolymer (including all ofrandom copolymers, block copolymers, graft copolymers, etc.), isoprenepolymer, chlorobutadiene polymers, butadiene-acrylonitrile copolymer,isobutylene polymer, isobutylene-butadiene copolymer,isobutylene-isoprene copolymer, acrylate ester copolymer,ethylene-propylene copolymer, ethylene-butene copolymer,ethylene-propylene-diene copolymer, Thiokol rubber, polysulfide rubber,polyurethane rubber, polyether rubber e.g., polypropylene oxidc,epichlorohydrin rubber, polyester elastomer, polyamide elastomer, etc.

These rubber-like materials may be produced by any methods (e.g.,emulsion polymerization, solution polymerization, etc.) and with anycatalysts (e.g., peroxides, trialkylaluminum, lithium halides, nickelcatalysts).

Furthermore, there may be also used those which have variouscrosslinking degrees, various proportions of micro structures (e.g., cisstructure, trans structure, vinyl group, etc.) or various average rubberparticle sizes.

Various polymers such as random compolymers, block copolymers, graftcopolymers, etc. may be used as the copolymers for rubber-like materialsin this invention.

Modification of rubber-like materials may be effected by any methods ofintroduction of at least one mutual compatibilizer of low molecularweight mentioned above. Generally, this is effected by copolymerization(including all of random copolymerization, block copolymerization, graftcopolymerization, etc.) and raction with main chain, side chain andterminal of molecule.

Epoxy compound includes epoxy resin and precursors thereof and epoxygroup-containing copolymer. Examples of epoxy resin and its precursorsare bisphenol A epoxy resin, O-cresol novolac epoxy resin, glycidylamineepoxy resin, three-functional epoxy resin and four-functional epoxyresin. The epoxy compound may further contain a reactive diluent.

Epoxy group-containing copolymer includes, for example, unsaturatedepoxy compound/ethylenically unsaturated compound copolymer, epoxidizedpolyester and epoxidized polyamide. Unsaturated epoxy compound used forthe unsaturated epoxy compound/ethylenically unsaturated compoundcopolymer has in a molecule both an epoxy group and an unsaturated groupwhich is copolymerizable with the ethylenically unsaturated compound,for instance, unsaturated glycidyl ester and unsaturated glycidyl etherhaving the formulas (1) and (2) below: ##STR5## wherein R is a C₂ -C₁₈hydrocarbon group containing ethylenically unsaturated bond and X is--CH₂ --O-- or ##STR6##

Examples are glycidyl acrylate, glycidyl methacrylate, glycidylitaconate, allylglycidyl ether, 2-methylallyl glycidyl ether,styrene-p-glycidyl ether. The ethylenically unsaturated compound isolefin, vinyl ester of C₂ -C₆ saturated carboxylic acid, C₁ -C₈saturated alcohol/acrylic or methacrylic acid ester, maleate,methacrylate, fumarate, halogenated vinyl, styrene, nitrile, vinyl etheror acrylamide. Examples are ethylene, propylene, butene-1, vinylacetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethylmalate, diethyl fumarate, vinyl chloride, vinylidene chloride, styrene,acrylonitrile, isobutyl vinyl ether and acrylamide. They are used singlyor in a mixture of at least two of them. Ethylene is preferable most ofall.

Composition ratio in the epoxy group-containing copolymer is notcritical, but 0.1-50% by weight, more preferably 1-30% by weight ofunsaturated epoxy compound is preferred.

The epoxy group-containing copolymer is prepared by various methods.Either random copolymerization or graft copolymerization may beeffected; in the former, unsaturated epoxy compound is introduced inbackbone chain of copolymer, and in the latter, unsaturated epoxycompound is introduced in side chain of copolymer. Examples arecopolymerization in which unsaturated epoxy compound is allowed to reactwith ethylene in the presence of a radical initiator under 500-4000 atm.at 100°-300° C. in the presence or absence of a solvent and a chaintransfer agent; graft copolymerization in which polypropylene,unsaturated epoxy compound and a radical initiator are blended andallowed to melt in an extruder; and copolymerization in whichunsaturated epoxy compound is allowed to react with ethylenicallyunsaturated compound in an inert solvent such as water or an organicsolvent in the presence of a radical initiator.

Copolymer of unsaturated epoxy compound/ethylenically unsaturatedcompound is preferable, particularly, copolymer of unsaturated epoxycompound/ethylene/other ethylenically unsaturated compound thanethylene.

Compositional ratio in the resin composition comprising (A) dispersingphase of polyphenylene ether, (B) crystalline thermoplastic matrix phaseand (C) mutual compatibilizer compatible with (A) and/or (B) ispreferably (A) 1-65%, (B) 35-98.9% and (C) 0.1-50%, more preferably (A)1-60%, (B) 40-98.9% and (C) 0.1-30% and most preferably (A) 1-60%, (B)40-98.9% and (C) 0.1-20% (wherein % is by weight). When (A) is less than1% by weight, the composition is inferior in heat resistance, dimensionstability and proecessability and when more than 65% by weight,dispersing phase is not formed and impact strength and processabilityare inferior. When (B) is less than 35% by weight, matrix phase is notformed and impact strength and processability are deteriorated. When (B)is more than 98.9% by weight, heat resistance, dimension stability,hygroscopicity and processability are not improved. When (C) is lessthan 0.1% by weight, the phases become unstable and impact strengthdecreases. When (C) is more than 50% by weight, gelation proceeds todeteriorate processability and besides, the matrix (B) is hardly formedand phase is unstable to reduce impact strength.

Average particle size in the polyphenylene ether dispersing phase (A) issuitably 0.01-10μ, preferably 0.05-5μ, more preferably 0.05-3μ. Furtherpreferred particle size is 0.1-2μ, more preferably 0.1-1.8μ. When theparticle size is outside the above range, impact strength decreases.

The resin composition of this invention may further contain (D) fibrousreinforcing composites having an aspect ratio (ratio of major axis andminor axis) of at least 10 such as glass fiber, carbon fiber, polyamidefiber and metallic whisker or (E) inorganic filler (excluding fibrousfiller) having an average particle size of 10μ or less such as silica,alumina, calcium carbonate, talc, mica, carbon black, TiO₂ and ZnO.

In case the fibrous reinforcing composite material (D) or the inorganicfiller (E) is added, addition amount thereof is 1-50 parts by weight per100 parts by weight of the resin composition comprising (A) dispersephase comprising polyphenylene ether, (B) crystalline thermoplasticresin matrix phase and (C) mutual compatibilizer.

One preferred embodiment of this invention may be to use the resincomposition in the form of composite material wherein flame retardantssuch as Sb₂ O₃ or flame retardant aids; lubricants; nuclear agents;plasticizers; dyes; pigments; antistatic agents; antioxidants;weatherability providing agents, etc. are added.

Any process is used to prepare the present resin composition.

Melt-blending methods for the components are the best from an economicalpoint of view, although it is possible to blend the components in asolution and evaporate the solvent or precipitate in a non-solvent.Melt-blending is carried out in a single-screw or a twin-screw extruder,a kneader or so, preferably a high-speed twin-screw extruder.

Before kneading, it is preferable to uniformly blend powder or pelletsof the component resins in a tumbler or a Henschel mixer. The firstblending above is not always necessary. Alternatively, each resin may befed to a kneader through a metering apparatus. Resin composition, afterkneaded, is molded according to injection, extrusion and the like.Alternatively, dry blending the resin materials at the injection orextrusion molding without prekneading and direct kneading are made inthe melt processing to produce a shaped article. Any order is used inthe kneading step. For example, compounds for (A) and (B), and (C) arekneaded together, or compounds for (A) and (B) are first kneaded before(C) is kneaded or compounds for (A) and (C) are first kneaded beforecompound for (B) is kneaded. However, it is not desirable to kneadcompounds for (B) and (C) and then add compound for (A), becausegellation occurs and desirable resin composition is not produced.

The resin composition of this invention is used as shaped articles,sheets, tubes, films, fibers, laminates, coating materials, etc. made byinjection molding or extrusion molding, especially as automobile partssuch as bumper, inverness, fender, trim, door panel, wheel cover, sideprotector, garnish, trunk lid, bonnet, roof, etc., interior and exteriormaterials and mechanical parts required to have heat resistance.Furthermore, the resin composition is used as parts for motor bicyclessuch as covering material, muffler cover, leg shield, etc. andelectrical and electronic parts such as housing, chassis, connector,base for printed circuit, pulley and other parts required to havestrength and heat resistance.

This invention is explained referring to examples below, wherein theyare merely illustrative ones and this invention is not limited to them.Heat distortion temperature test (H.D.T.), Izod impact strength test(3.2 mm thick) and M.I. are observed in accordance with JIS K7207, JISK7110 and JIS K7210, respectively.

Polyphenylene ether, epoxy compounds and modified rubber-like materialsused in the examples and comparative examples are obtained below.Crystalline thermoplastic resins and epoxy resins for the epoxycompounds which are commercially available are used.

(1) Polyphenylene ether

Manganese chloride/ethylenediamine is added to a solution of2,6-dimethylphenol in toluene and methanol and then the solution issubjected to oxidation polymerization under a molecular oxygenatmosphere at 30° C.

(2) Modified rubber-like material

A mixture of ethylenepropylene rubber, maleic anhydride and tert-butylperoxylaurate is extruded from an extruder (screw diameter: 30 mm;L/D=28; barrel temperature: 230° C.; screw rotation: 60 rpm). Modifiedrubber strands extruded are cooled in water and pelletized.

(3) Epoxy compound

Glycidyl methacrylate/ethylene/vinyl acetate copolymer is prepared inaccordance with Japanese Patent Publications (Kokai) 47-23490 and48-113883. That is, glycidyl methacryalte, ethylene, vinyl acetate, aradical initiator and a chain-transfer agent are successively fed in areactor (40 l) made of stainless steel whose temperature is controlableand which is equipped with an inlet, an outlet and a stirrer, andcopolymerization is effected under stirring under 1400-1600 atm. at180°-200° C.

(4) Polyamide

Polyamide 6,6: UBE Nylon® 2020B (Ube Industries, Ltd.)

Polyamide 6: UBE Nylon® 1013B (Ube Industries, Ltd.)

(5) Polyester

Polybutylene terephthalate: TUFPET® N-1000 (Mitsubishi Rayon Co., Ltd.)

Polyethylene terephthalate: UNITIKA Polyester MA2101 (Unitika, Ltd.)

(6) Epoxy resin

SUMIEPOXY® ELM-434 (Sumitomo Chemical Co., Ltd.); 4-functional epoxyresin, epoxy equivalent=110-130 g/eq.

(7) Oleic acid amide

DENON SL-1® (Marubishi Petrochemical Co., Ltd.)

EXAMPLE 1

40 wt % of polyphenylene ether ηsp/c=0.47 dl/g (reduced viscositymeasured in 0.5 g/dl chloroform at 25° C.), 50 wt % of polyamide 66 "UBENylon"® 2020B and 10 wt % of maleic anhydride grafted ethylene propylenerubber (amount of maleic anhydride grafted: 0.7 wt % of ethylenepropylene rubber) were melted and kneaded at resin temperature of 310°C. and screw rotation of 500 rpm in a cotinuous twin-screw kneader(TEX-44® of Nippon Steel Manufacturing Co. Ltd.) and the product wasgranulated and test specimen were made therefrom by an injection moldingmachine (IS-150 of Toshiba Co.). Properties of the test specimen weremeasured The results are shown in Table 1.

An Izod impact strength test specimen before subjected to the test wassubjected to finishing on its cross section by microtome and dipped incarbon tetrachloride which is good solvent for polyphenylene ether for30 minutes at room temperature to etch polyphenylene ether. This testspecimen was examined by a scanning type electron microscope to measurediameter of dispersed particles of polyphenylene ether. Weight averageparticle size was calculated on the basis of maximum size of eachparticle. The results are also shown in Table 1.

COMPARATIVE EXAMPLE 1

Example 1 was repeated except that polyphenylene ether of ηsp/c=0.25 wasused. The results are shown in Table 1.

EXAMPLE 2

One part by weight of an epoxy resin "SUMIEPOXY ELM-434"® as acompatibilizing agent was added to 100 parts by weight of a compositioncomprising 50 wt % of polyphenylene ether of ηsp/c=0.51 and 50 wt % ofpolyethylene butylene terephthalate "TUFPET® BPT N-1000 and the mixturewas melted and kneaded at 360° C. in a small batchwise twin-screwkneader ("LABOPLASTMIL"® of Toyo Seiki Co.) at a screw rotation of 90rpm for 5 minutes. The resulting composition was pressed at 270° C. toprepare test specimen for Izod impact strength test and heat distortiontemperature test. Results of measurement of properties and averagedispersed particle diameter of polhphenylene ether measured by themethod of Example 1 are shown in Table 2.

COMPARATIVE EXAMPLE 2

Example 2 was repeated except that one part by weight of oleic acidamide "DENON SL-1"® (Marubishi Petrochemical Co.) was used in place ofthe epoxy resin as a compatibilizing agent. The results are shown inTable 2.

EXAMPLE 3

Example 2 was repeated using 30 wt % of polyphenylene ether (ηsp/c=0.55) 56 wt % of polyethylene terephthalate "UNITIKA PET" MA2101® and14 wt % of glycidyl methacrylate-ethylene-vinyl acetate (GMA-E-VA)copolymer. Results of measurement of properties and average dispersedparticle diameter are shown in Table 3.

COMPARATIVE EXAMPLE 3

First, 80 wt % of "UNITIKA PET" MA2101® (polyetheylen terephthalate) and20 wt % of GMA-E-VA copolymer which were the same as used in Example 3were melted and kneaded in "LABOPLASTMIL"® and then 70 wt % of theresulting composition and 30 wt % of the same polyphenylene ether asused in Example 3 were further kneaded and molded and properties weremeasured as in Example 3. The results are shown in Table 3.

EXAMPLE 4

Example 2 was repeated using 40 wt % of polyphenylene ether(ηsp/c=0.52), 50 wt % of polyamide 6 "UBE Nylon"® 1013B and 10 wt % ofmaleic anhydride grafted ethylene propylene rubber. The results areshown in Table 4.

EXAMPLE 5

Example 4 was repeated except that polyamide 66 "UBE Nyon"® 2020B wasused in place of polyamide 6. The results are shown in Table 4.

From these examples and comparative examples, it will be seen that Izodimpact strength increases with decrease in average particle diameter ofdisperse phase comprising polyphenylene ether and decreases to apractically unacceptable value when the particle diameter exceeds 10μand thus the particle diameter of disperse phase of polyphenylene etheris an important factor.

It has been found that this dispersed particle diameter varies dependingon molecular weight of polyphenylene ether, kind of the compatibilizingagent and kneading method. These are surprising facts unexpectable fromthe conventional technique on polyphenylene ether composition.

EXAMPLE 6

Example 1 was repeated except that polyphenylene ether of ηsp/c=0.55 wasused. The results are shown in Table 1.

EXAMPLE 7

Example 1 was repeated except that polyphenylene ether of ηsp/c=0.57 wasused. The results are shown in Table 1. Surprisingly, it is seen fromTable 1 that reduced viscosity of polyphenylene ether has a suitablerange and when it is less than 0.40, diameter of dispersed particlesincreases to cause reduction of Izod impact strength and when it reaches0.60, the diameter also tends to increase.

EXAMPLE 8

40 wt % of polyphenylene ether (ηsp/c=0.47 dl/g), 50 wt % of polyamide66 "UBE Nylon"® 2020B and 10 wt % of maleic anhydride grafted ethylenepropylene rubber (amount of maleic anhydride: 97 wt % of the ethylenepropylene rubber) were kneaded at 260° C. for 5 minutes in a smallbatchwise twin-screw kneader "LABOPLASTMIL"® at a screw rotation of 90rpm. The resulting composition was pressed (270° C.) to produce testspecimens and properties thereof were measured. The results are shown inTable 5.

EXAMPLE 9

Example 8 was repeated except that the kneading was effected at 280° C.The results are shown in Table 5.

It is recognized from Examples 8 and 9 that even if composition is thesame, particle diameter of disperse phase of polyphenylene ether changesand further impact strength markedly changes with change in kneadingconditions. That is, importance of diameter of dispersed particles isclearly shown.

EXAMPLE 10

Example 6 was repeated except that amount of polyamide 66 was changed to45 wt % and that of glycidyl methacrylate-ethylene-vinyl acetatecopolymer (content of glycidyl methacrylate: 10 wt % of the copolymer)was changed to 5 wt %. The results are shown in Table 1.

EXAMPLE 11

50 wt % of polyphenylene ether (ηsp/c=0.47 dl/g), 10 wt % of maleicanhydride grafted ethylene propylene rubber (amount of maleic anhydridegrafted: 0.7 wt % of ethylene propylene rubber) and 0.6 part by weight(based on the total composition) of maleic anhydride were introducedinto a twin-screw continuous kneader ("TEX-44"® Nippon SteelManufacturing Co., Ltd.) from its first hopper and 40 wt % of polyamide6 "UBE Nylon"® 1013B was introduced from second hopper provided betweenthe first hopper and vent hole and they were melted and kneaded at resintemperature of 310° C.-340° C. and a screw rotation of 380 rpm and thengranulated. Then, test specimens were made by an injection moldingmachine (IS-150E of Toshiba Machine Co., Ltd.) and properties weremeasured. The results are shown in Table 6.

EXAMPLE 12

Example 11 was repeated except that ethylene propylene rubber was usedin place of maleic anhydride grafted ethylene propylene rubber. Theresults are shown in Table 6.

EXAMPLE 13

Example 12 was repeated except that 10 wt % of 2-vinyl-2-oxazolinegrafted polystyrene ("RPS"® Dow Chemical Co.) was used in place of 0.6part by weight of the maleic anhydride and amount of polyphenylene etherwas changed to 40 wt %. The results are shown in Table 6.

                                      TABLE 1                                     __________________________________________________________________________                                                      Average                                                             Izod      particle                    A           B       C               M.I.                                                                              Impact    diameter of                 Polypheny-  Polyamide                                                                             Modified rubber                                                                        Epoxy group                                                                          280° C.                                                                    (notched)                                                                          H.D.T.                                                                             polyphenylene               lene        UBE Nylon ®                                                                       Maleic anhydride                                                                       containing                                                                           10 Kg                                                                             Kg · cm/                                                                  (18.6                                                                              ether                       ether       2020B   grafted EPR                                                                            copolymer                                                                            load                                                                              cm   Kg/cm.sup.2)                                                                       (μ)  Note                __________________________________________________________________________    Example 1                                                                           40 wt %                                                                             50 wt % 10 wt %  -- wt %                                                                              8.5 12.3 119.1                                                                              2.0     PPE                                                                           ηsp/c =                                                                   0.47                Compara-                                                                            40    50      10       --     49.0                                                                              4.8  114.9                                                                              15.0    PPE                 tive                                                      ηsp/c =         Example 1                                                 0.25                Example 6                                                                           40    50      10       --     7.0 8.9  115.4                                                                              2.7     PPE                                                                           ηsp/c =                                                                   0.55                Example 7                                                                           40    50      10       --     7.0 6.5  114.9                                                                              2.9     PPE                                                                           ηsp/c =                                                                   0.57                Example 10                                                                          40    45      10       *GMA-E-                                                                              2.7 15.1 108.2                                                                              1.9     PPE                                              VA                           ηsp/c =                                      copolymer                    0.55                                             5                                                __________________________________________________________________________     *GMA: Glycidyl methacrylate,                                                  E: Ethylene,                                                                  VA: Vinyl acetate                                                        

                                      TABLE 2                                     __________________________________________________________________________                                  M.I.                                                                              Izod        Average particle                       A       B      C       280° C.                                                                    Impact H.D.T.                                                                             diameter of                            Polyphenylene                                                                         Polybutylene                                                                         Compatibilizing                                                                       10 Kg                                                                             (notched)                                                                            (18.6                                                                              polyphenylene                          ether   terephthalate                                                                        agent   load                                                                              Kg · cm/cm                                                                  Kg/cm.sup.2)                                                                       ether (μ)                    __________________________________________________________________________    Example 2                                                                            50 wt % 50 wt %                                                                              *Part of weight                                                                        4.9                                                                              7.7    170.1                                                                              10.0                                                   Epoxy resin                                                                   1                                                      Comparative                                                                          50      50      Oleic amide                                                                          31.2                                                                              3.7    162.0                                                                              46.8                            Example 2              1                                                      __________________________________________________________________________     *Amount per 100 parts by weight of (A + B)                               

                                      TABLE 3                                     __________________________________________________________________________                          C       M.I.                                                                              Izod        Average particle                       A       B      Epoxy group                                                                           280° C.                                                                    Impact H.D.T.                                                                             diameter of                            Polyphenylene                                                                         Polyethylene                                                                         containing                                                                            10 Kg                                                                             (notched)                                                                            (18.6                                                                              polyphenylene                          ether   terephthalate                                                                        copolymer                                                                             load                                                                              Kg · cm/cm                                                                  Kg/cm.sup.2)                                                                       ether (μ)                    __________________________________________________________________________    Example 3                                                                            30 wt % 56 wt %                                                                              GMA-E-VA                                                                              1.15                                                                              5.7     84   5.4                                                  copolymer                                                                     14 wt %                                                 Comparative                                                                          30      56     same as above                                                                         96.7                                                                              2.3    112  12.8                            Example 3             14                                                                     .BHorizBrace.                                                                 First stage formation                                                         of master batch                                                __________________________________________________________________________     *At the first stage, PET/GMA copolymer = 56/14 wt % and polyethylene          terephthalate were melted and kneaded and then at the second stage 70 wt      of this composition and 30 wt % of PPE were melted and kneaded.          

                                      TABLE 4                                     __________________________________________________________________________                        C        M.I. Izod        Average particle                A                   Modified rubber                                                                        280° C.                                                                     Impact H.D.T.                                                                             diameter of                     Polyphenylene B     Maleic anhydride                                                                       2.16 Kg                                                                            (notched)                                                                            (18.6                                                                              polyphenylene                   ether         Polyamide                                                                           grafted rubber                                                                         load Kg · cm/cm                                                                  Kg/cm.sup.2)                                                                       ether (μ)                    __________________________________________________________________________    Example 4                                                                           40 wt % UBE   10 wt %  15.8 8.8    110  8.7                                           Nylon ®                                                                   1013B                                                                         50 wt %                                                         Example 5                                                                           40      UBE   10       0.1  19.9   112.5                                                                              1.8                                           Nylon ®                                                                   2020B                                                                         50 wt %                                                         __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________                  B       C                 Izod   Average particle               A             Polyamide                                                                             Modified rubber   Impact diameter of                    Polyphenylene UBE Nylon ®                                                                       Maleic anhydride                                                                       Kneading (notched)                                                                            polyphenylene                  ether         2020B   grafted rubber                                                                         conditions                                                                          M.I.                                                                             Kg · cm/cm                                                                  ether (μ)                   __________________________________________________________________________    Example 8                                                                           40 wt % 50 wt % 10 wt %  260° C.                                                                      15.5                                                                             18.7   1.9                                                           90 rpm                                                                        5 min.                                         Example 9                                                                           40      50      10       280° C.                                                                      15.9                                                                             10.1   2.5                                                           90 rpm                                                                        5 min.                                         __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________                                         M.I. Izod       Average particle                A       B         C           280° C.                                                                     Impact     diameter of                     Polyphenylene                                                                         Polyamide UBE   Maleic                                                                              10 Kg                                                                              (notched)                                                                            H.D.T.                                                                            polyphenylene                   ether   Nylon ® 1013B                                                                       Rubber                                                                              anhydride                                                                           load Kg · cm/cm                                                                  (°C.)                                                                      ether                    __________________________________________________________________________                                                         (μ)                   Example 11                                                                           50 wt % 40 wt %   Maleic                                                                              part by                                                                             45   54     115 0.5                                               anhydride                                                                           weight                                                                  grafted                                                                             0.6                                                                     rubber                                                                        10 wt %                                              Example 12                                                                           50      40        Ethylene                                                                            part by                                                                             47   53     117 0.6                                               propy-                                                                              weight                                                                  lene  0.6                                                                     rubber                                                                        10 wt %                                              Example 13                                                                           40      40        Ethylene                                                                            "RPS" 50   53     115 1.0                                               propy-                                                                              10 wt %                                                                 lene                                                                          rubber                                                                        10 wt %                                              __________________________________________________________________________

It has been found from the above examples and comparative examples thatin composition of polyphenylene ether, crystalline thermoplastic resinand mutual compatibilizer , particle diameter of dispersing phase of thepolyphenylene ether has conspicuous effects on impact strength and isdesirably 0.01-10μ, preferably 0.05-5μ, more preferably 0.05-3μ, furtherpreferably 0.1-2μ, the most preferably 0.1-1.8μ.

As explained above, the resin composition of this invention comprises adispersing phase consisting polyphenylene ether, a crystallinethermoplastic resin and a mutual compatibilizer which is compatible withboth or either of the two phases.

Compatible with both or either one of said two phases and impactstrength of this composition which has not been able to improve byconventional technique can be improved without substantially noreduction in heat resistance by specifying particle diameter of thepolyphenylene ether dispers phase.

Especially, hitherto no attention has been given to the fact thatdiameter of dispersed particles in a composition containingpolyphenylene ether has a great effect on impact strength and so rubbercomponent must have been used in a large amount in order to improveimpact strength which is accompanied by reduction of heat resistance.

This invention can provide more readily a novel composition having asuperior balance between impact strength and heat resistance byspecifying particle diameter of disperse phase of polyphenylene ether,using a mutual compatibilizer which serves to obtain the specificparticle diameter and specifying molecular weight of polyphenyleneether.

The novel composition provided by this invention can be processed toshaped articles, sheet, film, tube, coating material by processingmethods employed for thermoplastic resins such as injection molding,extrusion molding, etc. to afford articles excellent in balance ofproperties such as heat resistance, impact strength, processability,dimension stability, etc.

We claim:
 1. A thermoplastic resin composition comprising:(A) adipersing phase of 1-65 percent by weight of polyphenylene ether havinga reduced viscosity of 0.4-0.60 measured in chloroform solution at 25°C. obtained by oxidation polymerization of at least one phenyl compoundrepresented by the formula: ##STR7## wherein R₁, R₂, R₃, R₄ and R₅ eachrepresent a hydrogen atom, a halogen atom or a substituted orunsubstituted hydrocarbon residues wherein at least one of R₁, R₂, R₃,R₄ and R₅ is a hydrogen atom, (B) a matrix phase of 35-98.9% by weightof polyamide resin, and (c) 0.1-50% by weight of a mutual compatibilizercompatible with (A) and (B), wherein the average particle size diameterin said dispersing phase (A) is 0.1-1.8 microns, and said mutualcompatibilizer (C) is at least one member selected from the groupconsisting of (C)(1) compound containing, in the molecule, at least onecarboxyl group, acid anhydride group, acid amide group, imide group,carboxylate group, amino group, isocyanate group, oxazolinering-containing group and hydroxyl group, (C)(2) epoxy compound and(C)(3) modified rubber-like material, obtained by modifying arubber-like material with at least one compound selected from (C)(1) and(C)(2), and wherein the thermoplastic composition is obtained bykneading firstly said dispersing phase (A) with said mutualcompatibilizer (C) and then thereafter said matrix phase (B) therewith.2. A resin composition according to claim 1 wherein said dispersingphase (A) said polyphenylene ether has a reduced viscosity of 0.45-0.55.3. A resin composition according to claim 1 wherein the epoxy compound(C)(2) is an unsaturated epoxy compound.
 4. A resin compositionaccording to claim 1 wherein said compound (C)(1) is at least one memberselected from the group consisting of acrylic acid, maleic acid, fumaricacid, maleic anhydride, maleic hydrazide and maleimide.
 5. A resincomposition according to claim 3 wherein said compound (C)(1) is atleast one member of the group consisting of acrylic acid, maleic acid,fumaric acid, maleic anhydride, maleic hydrazide and maleimide.
 6. Aresin composition according to claim 1 wherein said epoxy compound(C)(2) is an epoxy resin.
 7. A resin composition according to claim 1wherein said epoxy compound (C)(2) is at least one member of the groupconsisting of (i) of copolymer comprising ethylene and an unsaturatedepoxy compound and (ii) a copolymer comprising ethylene, an unsaturatedepoxy compound and an ethylenically unsaturated compound having morethan two carbon atoms.
 8. A resin composition according to claim 1wherein amount of said dispersing phase (A) is 1-65% by weight, that ofsaid matrix phase (B) is 35-98.9% by weight and, that of said mutualcompatibilizer (C) is 0.1-50% by weight.